CN106315800A - Method for treating high-concentration chromium-containing wastewater through precipitation assisted with plants - Google Patents
Method for treating high-concentration chromium-containing wastewater through precipitation assisted with plants Download PDFInfo
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- CN106315800A CN106315800A CN201610721477.8A CN201610721477A CN106315800A CN 106315800 A CN106315800 A CN 106315800A CN 201610721477 A CN201610721477 A CN 201610721477A CN 106315800 A CN106315800 A CN 106315800A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for treating high-concentration chromium-containing wastewater through precipitation assisted with plants, and belongs to the technical field of wastewater treatment. The method comprises the steps that the plants rich in hydrophilic group are subjected to enzymolysis with a compound enzyme, a hydrophilic plant precipitating aid agent is obtained through ultrasonic alcohol extraction, Cr<6+> in the wastewater is reduced to Cr<3+> with ferrous sulfate, then calcium hydroxide is added and generates chromic hydroxide precipitates under the alkaline condition, and therefore chromium ions are removed. According to the method, in the chromic hydroxide precipitate generating process, on one hand, Fe<3+> generated in the process that Cr<6+> is reduced with ferrous sulfate adsorbs water molecules agglomerated around the chromium ions, and meanwhile water molecules agglomerated around the chromium ions are adsorbed through the plant precipitating aid agent and hyaluronic acid, the two methods are combined to act, when chromic hydroxide precipitates, crystals are gradually crystallized and become large, the crystallization rate is increased, chromic hydroxide precipitates rapidly to be flocculated into a big crystal nucleus, sedimentation is promoted, the precipitate reduction efficiency is improved, the treating process is simplified, chemical consumption is reduced, and the treatment cost is reduced.
Description
Technical field
The present invention relates to a kind of method that plant aids precipitation processes high-concentration chromium-containing wastewater, belong to wastewater processing technology neck
Territory.
Background technology
Chromium is a kind of main pollutant in environment, and its important sources is exactly electroplating wastewater.Along with science and technology
Development, the scale of electroplating industry is increasing, and the chromate waste water amount of discharge is consequently increased, if the most effectively processed,
Environment be will result in harm greatly.
Chromium valence state in water environment is more, mainly based on trivalent chromium and Cr VI.Chromic toxicity is relatively strong, is public
The carcinogen recognized, has high risks to human body.Trivalent chromium toxicity is more weak, is the required trace element of a kind of humans and animals.
For the chromium ion treatment technology leading with reduction precipitation method, the chromium hydroxide precipitation produced due to processing procedure is brilliant
Core is minimum, for the waste water especially for high chromium concentration ion, easily forms emulsion state precipitation, and settling velocity is extremely slow, impact
The efficiency of whole process technique.Up to standard for chromium ion, current technique is the most all the calcium hydroxide by adding surplus in a large number
Precipitating the chromium ion removing waste water, dosage seldom carries out quantitatively according to the content of chromium ion that waste water is actual, and on the one hand this make
Become the waste of Calcium Salt Reagents, economical difference, additionally the more important thing is that the calcium salt of surplus adds the salinity significantly increasing waste water,
Original salinity is made to strengthen with regard to the biochemical treatment difficulty of of a relatively high chromate waste water.
Summary of the invention
The technical problem that present invention mainly solves, the chromium ion treatment technology dominated for current reduction precipitation method, due to
The chromium hydroxide precipitation nucleus that processing procedure produces is minimum, for the waste water especially for high chromium concentration ion, is easily formed
Emulsion state precipitates, and settling velocity is extremely slow, the problem affecting the efficiency of whole process technique, it is provided that at a kind of plant aids precipitation
The method of reason high-concentration chromium-containing wastewater.The method first uses complex enzyme zymohydrolysis rich in the plant of hydrophilic group, is raised by ultrasonic alcohol
Heavy liquid is helped to hydrophilic plant, then with ferrous sulfate by the Cr in waste water6+It is reduced into Cr3+, then add calcium hydroxide, make
It generates chromium hydroxide precipitation in the basic conditions, thus removes chromium ion, and the present invention is being formed during chromium hydroxide precipitation,
On the one hand Cr is reduced by ferrous sulfate6+Shi Shengcheng Fe3+The hydrone reunited around chromium ion is adsorbed, leads to again simultaneously
Cross plant settling agent and the hydrone reunited around chromium ion is adsorbed by the hyaluronic acid rich in hydrophilic carboxylic hydroxyl, both
Compound action, when making chromium hydroxide precipitation, hydrone will not be reunited around chromium ion, and crystal is able to Step crystallization and becomes big, carries
Its crystalline rate high and efficiency, make chromic oxide gel rapid precipitation flocculate into big nucleus, is conducive to sedimentation, improves precipitate reduction
Efficiency, simplifies processing procedure, saves chemical cost, reduces processing cost.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) count by weight, weigh 300～400 parts of wheel blade watermifoils, 400～500 portions of Fructus Ananadis comosis, 100～200 portions of Auricularia
With 200～400 parts of waterweeds be sequentially loaded in stone mortar after deionized water rinsing 3～5 times smash to pieces 10～15min obtain pasty state mix
Compound, loads enzymatic vessel by the pasty mixture obtained, and adds 3～5 parts of neutral protease, 1～2 part of lipase in enzymatic vessel
Mass concentration isopyknic with pasty mixture is 60% ethanol solution, is incubated enzymolysis 6～7h at 25～35 DEG C；
(2) after enzymolysis terminates, take out enzymatic hydrolysate put into sonic oscillation instrument with 200～300W oscillation of powers extraction 20～
Filter removal filtering residue after 30min and obtain filtrate, then filtrate is moved in centrifuge with 3000～4000r/min rotating speed centrifugal treating
10～15min, isolated supernatant i.e. obtains self-control plant and helps heavy liquid, standby；
(3) dig build one long 20 meters, wide 10 meters, deep 3 meters and bottom with the process pond of aerator, by high-concentration chromium-containing wastewater
In introducing pond, be that 500mg/L puts into ferrous sulfate powder in waste water by dosage, start aerator at the bottom of pond, aeration 3～
Stop after 5min；
(4) in pond, calcium hydroxide powder is added after aeration terminates again, until wastewater pH is to 8.0～8.5, then by above-mentioned standby
Self-control plant helps heavy liquid to add in waste water, and addition is 5～7mL/L, after starting aerator continuation Air Exposure 30～40min
Adding hyaluronic acid again in waste water, addition is 0.5～0.8mL/L, staticly settles 15～20min, extraction after addition
The supernatant, removes lower sediment；
(5) it is to continue after the supernatant of the upper strata biogas slurry in fowl and animal excrement methane-generating pit and above-mentioned extraction is mixed by 1:5 by volume
Be passed through and dig in the process pond built, after Air Exposure 15～20min stand 10～15min water outlets, can complete to high concentration containing every
The process of waste water.
The principle of the present invention is: the present invention, during forming chromium hydroxide precipitation, is on the one hand reduced by ferrous sulfate
Cr6+Shi Shengcheng Fe3+The hydrone reunited around chromium ion is adsorbed, the most again by plant settling agent with rich in hydrophilic
Property carboxylic hydroxyl hyaluronic acid the hydrone reunited around chromium ion is adsorbed, both compound actions, make chromic oxide gel sink
During shallow lake, hydrone will not be reunited around chromium ion, and crystal is able to Step crystallization and becomes big, improves its crystalline rate and efficiency, makes
Chromic oxide gel rapid precipitation flocculates into big nucleus, is conducive to sedimentation, improves the effect of precipitate reduction.
The invention has the beneficial effects as follows:
(1) processing method that the present invention provides improves treatment effeciency, after testing, the chromate waste water after process, Cr6+Concentration
It is down to 4～5mg/L, Cr by original 430～450mg/L6+Clearance reach more than 98.8%；
(2) processing method that the present invention provides simplifies processing procedure, saves chemical cost, reduces processing cost.
Detailed description of the invention
Count by weight, weigh 300～400 parts of wheel blade watermifoils, 400～500 portions of Fructus Ananadis comosis, 100～200 portions of Auricularia
With 200～400 parts of waterweeds be sequentially loaded in stone mortar after deionized water rinsing 3～5 times smash to pieces 10～15min obtain pasty state mix
Compound, loads enzymatic vessel by the pasty mixture obtained, and adds 3～5 parts of neutral protease, 1～2 part of lipase in enzymatic vessel
Mass concentration isopyknic with pasty mixture is 60% ethanol solution, is incubated enzymolysis 6～7h at 25～35 DEG C；Treat that enzymolysis is tied
Shu Hou, takes out enzymatic hydrolysate and puts into sonic oscillation instrument to filter removal filtering residue after 200～300W oscillation of power extractions 20～30min
Obtain filtrate, then filtrate is moved in centrifuge with 3000～4000r/min rotating speed centrifugal treating 10～15min, isolated
Supernatant i.e. obtains self-control plant and helps heavy liquid, standby；Dig and build one long 20 meters, wide 10 meters, deep 3 meters and bottom be with aerator
Process pond, high-concentration chromium-containing wastewater is introduced in pond, be that 500mg/L puts into ferrous sulfate powder in waste water by dosage, open
Aerator at the bottom of dynamic pond, stops after aeration 3～5min；Aeration adds calcium hydroxide powder after terminating again in pond, until waste water
PH to 8.0～8.5, more above-mentioned standby self-control plant helps heavy liquid add in waste water, addition is 5～7mL/L, starts aeration
Device adds hyaluronic acid after continuing Air Exposure 30～40min again in waste water, and addition is 0.5～0.8mL/L, has added
Staticly settle 15～20min after Biing, extract the supernatant, remove lower sediment；It is that 1:5 is by fowl and animal excrement methane-generating pit by volume
In upper strata biogas slurry and above-mentioned extraction supernatant mixing after continue to be passed through and dig in the process pond built, Air Exposure 15～20min
The water outlet of rear standing 10～15min, can complete high concentration containing the process every waste water.
Example 1
Count by weight, weigh 300 parts of wheel blade watermifoils, 400 portions of Fructus Ananadis comosis, 100 portions of Auricularia and 200 parts of waterweeds spend from
Sub-water rinses to be sequentially loaded in stone mortar after 3 times and smashs 10min to pieces and obtain pasty mixture, and the pasty mixture that will obtain loads enzymolysis
Tank, adding 3 parts of neutral protease, 1 part of lipase and the isopyknic mass concentration of pasty mixture in enzymatic vessel is 60% ethanol
Solution, is incubated enzymolysis 6h at 25 DEG C；After enzymolysis terminates, take out enzymatic hydrolysate and put into sonic oscillation instrument with 200W oscillation of power
Filter removal filtering residue after extraction 20min and obtain filtrate, then filtrate is moved in centrifuge with 3000r/min rotating speed centrifugal treating
10min, isolated supernatant i.e. obtains self-control plant and helps heavy liquid, standby；Dig and build one long 20 meters, wide 10 meters, deep 3 meters and bottom
With the process pond of aerator, high-concentration chromium-containing wastewater is introduced in pond, be that 500mg/L puts into sulfur in waste water by dosage
The ferrous powder of acid, starts aerator at the bottom of pond, stops after aeration 3min；Aeration adds calcium hydroxide powder after terminating again in pond
End, until wastewater pH is to 8.0, then helps heavy liquid to add in waste water by above-mentioned standby self-control plant, and addition is 5mL/L, starts
Aerator adds hyaluronic acid after continuing Air Exposure 30min again in waste water, and addition is 0.5mL/L, after addition
Staticly settle 15min, extract the supernatant, remove lower sediment；It is that 1:5 is by the upper strata in fowl and animal excrement methane-generating pit by volume
Continuing to be passed through after the supernatant mixing of biogas slurry and above-mentioned extraction digs in the process pond built, and stands 10min and go out after Air Exposure 15min
Water, can complete high concentration containing the process every waste water.
After testing, the chromate waste water after process, Cr6+Concentration be down to 4mg/L, Cr by original 430mg/L6+Removal
Rate reaches 99.06%.
Example 2
Count by weight, weigh 350 parts of wheel blade watermifoils, 450 portions of Fructus Ananadis comosis, 150 portions of Auricularia and 300 parts of waterweeds spend from
Sub-water rinses to be sequentially loaded in stone mortar after 4 times and smashs 13min to pieces and obtain pasty mixture, and the pasty mixture that will obtain loads enzymolysis
Tank, adding 4 parts of neutral protease, 1 part of lipase and the isopyknic mass concentration of pasty mixture in enzymatic vessel is 60% ethanol
Solution, is incubated enzymolysis 6h at 30 DEG C；After enzymolysis terminates, take out enzymatic hydrolysate and put into sonic oscillation instrument with 250W oscillation of power
Filter removal filtering residue after extraction 25min and obtain filtrate, then filtrate is moved in centrifuge with 3500r/min rotating speed centrifugal treating
13min, isolated supernatant i.e. obtains self-control plant and helps heavy liquid, standby；Dig and build one long 20 meters, wide 10 meters, deep 3 meters and bottom
With the process pond of aerator, high-concentration chromium-containing wastewater is introduced in pond, be that 500mg/L puts into sulfur in waste water by dosage
The ferrous powder of acid, starts aerator at the bottom of pond, stops after aeration 4min；Aeration adds calcium hydroxide powder after terminating again in pond
End, until wastewater pH is to 8.3, then helps heavy liquid to add in waste water by above-mentioned standby self-control plant, and addition is 6mL/L, starts
Aerator adds hyaluronic acid after continuing Air Exposure 35min again in waste water, and addition is 0.7mL/L, after addition
Staticly settle 18min, extract the supernatant, remove lower sediment；It is that 1:5 is by the upper strata in fowl and animal excrement methane-generating pit by volume
Continuing to be passed through after the supernatant mixing of biogas slurry and above-mentioned extraction digs in the process pond built, and stands 13min and go out after Air Exposure 18min
Water, can complete high concentration containing the process every waste water.
After testing, the chromate waste water after process, Cr6+Concentration be down to 4mg/L, Cr by original 450mg/L6+Removal
Rate reaches 99.11%.
Example 3
Count by weight, weigh 400 parts of wheel blade watermifoils, 500 portions of Fructus Ananadis comosis, 200 portions of Auricularia and 400 parts of waterweeds spend from
Sub-water rinses to be sequentially loaded in stone mortar after 5 times and smashs 15min to pieces and obtain pasty mixture, and the pasty mixture that will obtain loads enzymolysis
Tank, adding 5 parts of neutral protease, 2 parts of lipases and the isopyknic mass concentration of pasty mixture in enzymatic vessel is 60% ethanol
Solution, is incubated enzymolysis 7h at 35 DEG C；After enzymolysis terminates, take out enzymatic hydrolysate and put into sonic oscillation instrument with 300W oscillation of power
Filter removal filtering residue after extraction 30min and obtain filtrate, then filtrate is moved in centrifuge with 4000r/min rotating speed centrifugal treating
15min, isolated supernatant i.e. obtains self-control plant and helps heavy liquid, standby；Dig and build one long 20 meters, wide 10 meters, deep 3 meters and bottom
With the process pond of aerator, high-concentration chromium-containing wastewater is introduced in pond, be that 500mg/L puts into sulfur in waste water by dosage
The ferrous powder of acid, starts aerator at the bottom of pond, stops after aeration 5min；Aeration adds calcium hydroxide powder after terminating again in pond
End, until wastewater pH is to 8.5, then helps heavy liquid to add in waste water by above-mentioned standby self-control plant, and addition is 7mL/L, starts
Aerator adds hyaluronic acid after continuing Air Exposure 40min again in waste water, and addition is 0.8mL/L, after addition
Staticly settle 20min, extract the supernatant, remove lower sediment；It is that 1:5 is by the upper strata in fowl and animal excrement methane-generating pit by volume
Continuing to be passed through after the supernatant mixing of biogas slurry and above-mentioned extraction digs in the process pond built, and stands 15min and go out after Air Exposure 20min
Water, can complete high concentration containing the process every waste water.
After testing, the chromate waste water after process, Cr6+Concentration be down to 5mg/L, Cr by original 450mg/L6+Removal
Rate reaches 98.88%.
Claims (1)
1. the method that a plant aids precipitation processes high-concentration chromium-containing wastewater, it is characterised in that concrete operation step is:
(1) count by weight, weigh 300～400 parts of wheel blade watermifoils, 400～500 portions of Fructus Ananadis comosis, 100～200 portions of Auricularia
With 200～400 parts of waterweeds be sequentially loaded in stone mortar after deionized water rinsing 3～5 times smash to pieces 10～15min obtain pasty state mix
Compound, loads enzymatic vessel by the pasty mixture obtained, and adds 3～5 parts of neutral protease, 1～2 part of lipase in enzymatic vessel
Mass concentration isopyknic with pasty mixture is 60% ethanol solution, is incubated enzymolysis 6～7h at 25～35 DEG C；
(2) after enzymolysis terminates, take out enzymatic hydrolysate put into sonic oscillation instrument with 200～300W oscillation of powers extraction 20～
Filter removal filtering residue after 30min and obtain filtrate, then filtrate is moved in centrifuge with 3000～4000r/min rotating speed centrifugal treating
10～15min, isolated supernatant i.e. obtains self-control plant and helps heavy liquid, standby；
(3) dig build one long 20 meters, wide 10 meters, deep 3 meters and bottom with the process pond of aerator, by high concentration cadmium wastewater
In introducing pond, be that 500mg/L puts into ferrous sulfate powder in waste water by dosage, start aerator at the bottom of pond, aeration 3～
Stop after 5min；
(4) in pond, calcium hydroxide powder is added after aeration terminates again, until wastewater pH is to 8.0～8.5, then by above-mentioned standby
Self-control plant helps heavy liquid to add in waste water, and addition is 5～7mL/L, after starting aerator continuation Air Exposure 30～40min
Adding hyaluronic acid again in waste water, addition is 0.5～0.8mL/L, staticly settles 15～20min, extraction after addition
The supernatant, removes lower sediment；
(5) it is to continue after the supernatant of the upper strata biogas slurry in fowl and animal excrement methane-generating pit and above-mentioned extraction is mixed by 1:5 by volume
It is passed through and digs in the process pond built, stand 10～15min water outlets after Air Exposure 15～20min, can complete high concentration containing chromium
The process of waste water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610721477.8A CN106315800A (en) | 2016-08-25 | 2016-08-25 | Method for treating high-concentration chromium-containing wastewater through precipitation assisted with plants |
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| CN201610721477.8A CN106315800A (en) | 2016-08-25 | 2016-08-25 | Method for treating high-concentration chromium-containing wastewater through precipitation assisted with plants |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109374880A (en) * | 2018-09-30 | 2019-02-22 | 广西驰胜农业科技有限公司 | A kind of accurate detection method of tealeaves content of beary metal |
| CN109467226A (en) * | 2019-01-15 | 2019-03-15 | 临沂大学 | A kind of method of Cr VI in processing waste water |
| CN110104830A (en) * | 2019-05-20 | 2019-08-09 | 成都市农林科学院 | It is a kind of for handle pour tea place marsh liquid heavy metal content group technology |
| CN114635041A (en) * | 2022-04-01 | 2022-06-17 | 江西理工大学 | Method for removing chromium and vanadium from tungstate solution by using ferrous salt precipitation method |
-
2016
- 2016-08-25 CN CN201610721477.8A patent/CN106315800A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109374880A (en) * | 2018-09-30 | 2019-02-22 | 广西驰胜农业科技有限公司 | A kind of accurate detection method of tealeaves content of beary metal |
| CN109467226A (en) * | 2019-01-15 | 2019-03-15 | 临沂大学 | A kind of method of Cr VI in processing waste water |
| CN110104830A (en) * | 2019-05-20 | 2019-08-09 | 成都市农林科学院 | It is a kind of for handle pour tea place marsh liquid heavy metal content group technology |
| CN110104830B (en) * | 2019-05-20 | 2021-06-15 | 成都市农林科学院 | Combined process for treating heavy metal content of biogas slurry for irrigating tea garden |
| CN114635041A (en) * | 2022-04-01 | 2022-06-17 | 江西理工大学 | Method for removing chromium and vanadium from tungstate solution by using ferrous salt precipitation method |
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Application publication date: 20170111 |